ATOMIC STRUCTURE

All Bold Numbered Problems

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Chapter 7 Outline
Events leading to Quantum Mechanics Newton Planck Einstein Bohr de Broglie Schrdinger Heisenberg Using Quantum Numbers

ATOMIC STRUCTURE
From the ERA of

Newtonian Physics to
Quantum Physics

ELECTROMAGNETIC RADIATION

Electromagnetic Radiation
Most subatomic particles behave as PARTICLES and obey the physics of waves. Define properties of waves
Figure 7.1 and7.2.

Wavelength, Node Amplitude

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Figures 7.1
Electromagnetic Frequency

Electromagnetic Radiation
wavelength Visible light

There are
no
Amplitude

LIMITS
to ...

Wavelength () Ultraviolet radiation

Node

there are
an .
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Electromagnetic Radiation
wavelengt h Visible light

Amplitude

wavelengt h Ultaviolet radiation

Nod e

Node in a standing wave

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Electromagnetic Radiation
Waves have a frequency Use the Greek letter nu, , for frequency, and units are cycles per sec All radiation:

= c

where c = velocity of light = 3.00x108 m/sec

Long wavelength ----> small frequency

Short wavelength ----> high frequency
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Electromagnetic Radiation
Long wavelength -----> small frequency Short wavelength -----> high frequency

increasing frequency

increasing wavelength

See Figure 7.3

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Figure 7.3

Long wavelength -----> small frequency Short wavelength -----> high frequency
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Electromagnetic Radiation
Red light has = 700. nm. Calculate the frequency.
1 x 10 -9 m 700 nm = 7.00 x 10-7 m 1 nm
3.00 x 10 8 m/s 7.00 x 10
-7

Freq =

= 4.29 x 1014 sec -1

Examples
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Standing Waves
1st vibration = 2nd vibration = 2()

1st vibration

3rd vibration = 3()

2nd vibration

See Figure 7.4

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Newtonian Physics Breakdown -Quantization of EnergyIt was believed that like wave theory,

energy was also continuous.

Max Planck (1858-1947) Solved the ultraviolet catastrophe

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Figure 7.5
Intensity should Increase with Decreasing . As you add more energy, atoms should vibrate with a higher energy, in a continuous Objects can gain or fashion.

lose energy by absorbing or emitting radiant energy in QUANTA.

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Quantization of Energy
Energy of a vibrating system (electromagnetic radiation) is proportional to frequency.

Ep = h
h = Plancks constant = 6.6262 x 10-34 Js We now MUST abandon the idea that Energy acts as a continuous wave!

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From Planck on to Einstein

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Photoelectric Effect
A. Einstein (1879-1955) Experiment demonstrates the particle nature of light. (Figure 7.6) Classical theory said that E of ejected electron should increase with increase in light intensitynot observed! No e- observed until light of a certain minimum E is used & Number of e- ejected depends on light intensity.
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Photoelectric Effect
Experimental observations says that light consists of particles called PHOTONS having discrete energy. It takes a high energy particle to bump into an atom to knock its electron out, hence the use of a mv2 term. It would take some minimum energy i.e. critical energy to knock that electron away from its atom.

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Energy of Radiation
PROBLEM: Calculate the energy of 1.00 mole of photons of red light.
= 700. nm ( c = ) = 4.29 x 1014 sec-1

Ep = h
= (6.63 x 10-34 Js)(4.29 x 1014 sec-1)

= 2.85 x 10-19 J/photon Notice Einstein's use of Planck's formula.

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Energy of Radiation
Energy of 1.00 mol of photons of red light. Ep = h = (6.63 x 10-34 Js)(4.29 x 1014 sec-1) = 2.85 x 10-19 J per photon E per mol = (2.85 x 10-19 J/ph)(6.02 x 1023 ph/mol) = 171.6 kJ/mol This is in the range of energies that can break bonds.
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Photoelectric Effect
A minimum frequency is required to cause any current flow. Above that frequency, the current is related to the intensity of the light used. The ejected electrons (since we are talking about collisions between photons and electrons) also have more kinetic energy when higher frequencies are used.

EK =

1/2

meve2 = Einput - Eminimum

Einstein finds: Ep = h = 1/2 meve2, evidence that photons have both wave/particle properties
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Photoelectric Effect
Light is used to eject an electron from a metal. Calculate the velocity of the ejected electron if the photon used to eject the electron has a wavelength of 2.35 x 10 -7 m and the minimum frequency required to eject an electron is 8.45 x 10 14 s-1.
Step by step!!
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The Final Crack in Classical, Newtonian Physics MONUMENTAL Edifice

Planck---Energy is NOT Continuous like waves

Einstein---Energy comes in packets or is Quantized and energy also has some wave and particle behavior
Bohr---Applies Quantized idea to atomic particles.the H1 Atom to explain..
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Atomic Line Spectra and Niels Bohr

Bohrs greatest contribution to science was BUILDING a SIMPLE MODEL of the ATOM. It was based on an understanding of the LINE SPECTRA of excited atoms and its relationship to quantized energy.
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Niels Bohr (1885-1962)

Line Spectra of Excited Atoms

Excited atoms emit light of only certain wavelengths (Planck). The wavelengths of emitted light depend on the element.

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Figure 7.7

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Figure 7.8

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Figure 7.9

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Line Spectra of Excited Atoms

High E Short High Low E Long Low

Visible lines in H atom spectrum are

called the BALMER series.
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Shells or Levels!!

Why??

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Figure 7.12
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Excited Atoms Emit Light

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Atomic Spectra and Bohr

One view of atomic structure in early 20th century was that an electron (e-) traveled about the nucleus in an orbit. Electron

Orbit

1. Any orbit (like a wave-see slide 3) should be possible and so should any energy. 2. But a charged particle would always be accelerating from the nucleus (vector velocity is always changing) and since it is moving in an electric field would continuously emit energy. End result should be destruction since the energy mentioned in the previous step is finite!
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Atomic Spectra and Bohr

Bohr said classical (Newtonian) view is wrong!!!. Need a new theory now called QUANTUM or WAVE MECHANICS. e- can only exist in certain discrete orbits called stationary states. e- is restricted to QUANTIZED energy states.

Energy of state, En = - C/n2

where n = quantum no. = 1, 2, 3, 4, .... this describes the potential energy of an electron
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Atomic Spectra and Bohr

Energy of quantized state, En = - C/n2
Only orbits where n = integral numbers are permitted. Radius of allowed orbitals, Rn, Rn= n2 R0 with Ro = 0.0529 nm Note the same equations come from modern wave mechanics approach. Results can be used to explain atomic spectra.
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Atomic Spectra and Bohr

If e-s are in quantized energy states, then DE of states can have only certain values. This explain sharp line spectra.

E = -C ( 1/2 )

n=2

E = -C ( 1/1)

n=1
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Atomic Spectra and Bohr

E N E R G Y

E = -C ( 1 / 2 2 )

n=2

E = -C ( 1 / 1 2 )

n=1

Calculate DE for e- falling from high energy level (n = 2) to low energy level (n = 1).

DE = Efinal - Einitial = - C [ (1/1)2 - (1/2)2 ]

DE = - (3/4) C

Note that the process is exothermic!

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Atomic Spectra and Bohr

DE = - (3/4)C

E N E R G Y

E = -C ( 1 / 2 2 )

n=2

E = -C ( 1 / 1 2 )

n=1

C has been found from experiment and is proportional to RH, the Rydberg constant.

RHhc = C = 1312 kJ/mole. of emitted light = (3/4)C = 2.47 x 1015 sec-1 and = c/ = 121.6 nm
This is exactly in agreement with experiment!
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Line Spectra of Excited Atoms

DE = Efinal - Einitial = - RHhc [ (1/nfinal2) - (1/ninitial2) ] A photon of light with frequency 8.02 x 1013 s-1 is emitted from a hydrogen atom when it deexcites from the n = 8 level to the n = ? level. Calculate the final quantum number state of the electron.
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Atomic Line Spectra and Niels Bohr

Bohrs theory was a great accomplishment. Recd Nobel Prize, 1922 Problems with theory theory only successful for H and only 1e- systems He+, Li2+. introduced quantum idea artificially. However, Bohrs model does not explain many e- systems.So, we go on to QUANTUM or WAVE MECHANICS
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Niels Bohr (1885-1962)

Quantum or Wave Mechanics

de Broglie (1924) proposed that all moving objects have wave properties. For light: E = mc2 E = h = hc /
L. de Broglie (1892-1987)

Therefore, mc = h / and for particles

h = mv

(mass)(velocity) = h / ,
the wave-nature of matter.

Quantum or Wave Mechanics

Baseball (115 g) at 100 mph = 1.3 x 10-32 cm
e- with velocity = 1.9 x 108 cm/sec = 0.388 nm Experimental proof of wave properties of electrons

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Quantum or Wave Mechanics

Schrdinger applied idea of e- behaving as a wave to the problem of electrons in atoms.

He developed the
E. Schrdinger 1887-1961

WAVE EQUATION.

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Quantum or Wave Mechanics

Solution of the wave equation give a set of mathematical expressions called

WAVE FUNCTIONS, .
E. Schrodinger 1887-1961

Each describes an allowed energy state of an e-. Quantization is introduced naturally.

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WAVE FUNCTIONS,
is a function of distance and two angles. Each corresponds to an ORBITAL the region of space within which an electron is found. does NOT describe the exact location of the electron. 2 is proportional to the probability of finding an e- at a given point.

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Uncertainty Principle
Problem of defining nature of electrons in atoms solved by W. Heisenberg. Cannot simultaneously define the position and momentum (= mv) of an electron. We define e- energy exactly but accept limitation that we do not know exact position.
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W. Heisenberg 1901-1976

QUANTUM NUMBERS
Each orbital is a function of 3 quantum numbers:

n, l, and ml
Electrons are arranged in shells(levels) and subshells(sublevels).

n l ml

--> shell --> subshell --> designates an orbital within a subshell

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QUANTUM NUMBERS

Symbol n (major)

Values 1, 2, 3, ..

Description Orbital size and energy where E = - RHhc(1/n2) Orbital shape or type (subshell) Orbital orientation
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l (angular)

0, 1, 2, .. n-1

ml (magnetic)

- l..0..+ l

# of orbitals in subshell = 2 l + 1

All 4 Quantum Numbers

Principle quantum number (n) Azimuthal quantum number (l) Magnetic quantum number (m) Spin quantum number (s)

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Atomic Orbitals the result of Quantum Mechanics Calculations

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Shells and Subshells

When n = 1, then l = 0 and ml = 0 . Therefore, if n = 1, there is 1 type of subshell and that subshell has a single orbital. (ml has a single value ---> 1 orbital) This subshell is labeled s Each shell has 1 orbital labeled s, and it is SPHERICAL in shape.
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1s Orbital

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2s Orbital

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3s Orbital

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Atomic Orbitals the result of Quantum Mechanics Calculations

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p Orbitals
When n = 2, then l = 0 and 1 Therefore, in the n = 2 shell there are 2 types of orbitals 2 subshells For l = 0 ml = 0 this is an For l = 1

Typical p orbital

planar node

s subshell

ml = -1, 0, +1

this is a p subshell with 3 orbitals See Figure 7.16

When l = 1, there is a PLANAR NODE thru the nucleus.

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59

p Orbitals

A p orbital

The three p orbitals lie 90o apart in space

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2px Orbital

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2py Orbital

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2pz Orbital

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3px Orbital

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3py Orbital

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3pz Orbital

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d Orbitals
When n = 3, what are the values of l?

l = 0, 1, 2
and so there are 3 subshells in the shell. For l = 0, ml = 0 ---> s subshell with a single orbital

For l = 1, ml = -1, 0, +1
--->

p subshell with 3 orbitals

For l = 2, ml = -2, -1, 0, +1, +2 --->

d subshell with 5 orbitals

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d Orbitals
s orbitals have no planar node (l = 0) and so are spherical. p orbitals have l = 1, and have 1 planar node, and so are dumbbell shaped. This means d orbitals, ( l = 2) have 2 planar nodes

typical d orbital
planar node

planar node

See Figure 7.16

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3dxy Orbital

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3dxz Orbital

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3dyz Orbital

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3dz Orbital

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2 2 3dx - y

Orbital

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f Orbitals
When n = 4, l = 0, 1, 2, 3 so there are 4 subshells in the shell. For l = 0, ml = 0

---> s subshell with single orbital For l = 1, ml = -1, 0, +1

---> p subshell with 3 orbitals For l = 2, ml = -2, -1, 0, +1, +2 ---> d subshell with 5 orbitals

For l = 3, ml = -3, -2, -1, 0, +1, +2, +3 ---> f subshell with 7 orbitals
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Orbitals and Quantum Numbers

n
1 2 2 2 2

l
0 0 1 1 1

ml
0 0 1 0 -1 1s 2s 2p

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Orbitals and Quantum Numbers

n
3 3 3 3 3 3 3 3 3

l
0 1 1 1 2 2 2 2 2

ml
0 1 0 -1 2 1 0 -1 -2 3s 3p

3d

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Sample Problems
No 1. Is it possible to have a d orbital in level 1? Yes 2. Is it possible to have a 6s subshell? One 3. How many orbitals are in a 7s sublevel? 9 4. How many orbitals are possible if n = 3?
5. What type of orbital has the quantum numbers 5d a) n = 5, l = 2, ml = 1 3d b) n = 3, l = 2, ml =-1 6f c) n = 6, l = 3, ml = -3
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Practice Problems
1. Calculate the wavelength of a photon having an energy of 2.58 x 10-18 J. 2. In the hydrogen atom, which transition, 3 --> 2 or 2 --> 1, has the longer wavelength? 3. Calculate the wavelength of an object (mass = 545 lbs) with a speed of 45 miles/hour. 4. Give all possible sets of quantum numbers for 4p, 3d, and 5s. 5. How many orbitals are in the a. the third level? b. l = 3 sublevel?
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Practice Problems Answers

1. 7.71 x 10-8 3. 1.3 x 10-37 m 4. 4p 2. 3 --> 2 5. a) 9 b) 7

ml

4 1 1 4 1 0 4 1 -1 Problem 4 continued on next slide.

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Practice Problems Answers

3d

n
3 3 3 3 3

l
2 2 2 2 2 0

ml
2 1 0 -1 -2 0

5s

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Sample Problem
1. Calculate the frequency of light having a wavelength of 1 x 10-7m.

= c
1 x 10-7m . = 3.00 x 108 m/s

= 3 x 1015 /s
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Sample Problem
2. Calculate the wavelength of light having a frequency of 1.5 x 108 hz.

= c . 1.5 x 108 /s = 3.00 x 108 m/s

= 2.0 m
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Sample Problem
3. Calculate the frequency of light having a wavelength of 1 x 103nm.

= c
1 x 10-6m . = 3.00 x 108 m/s

= 3 x 1014 /s
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Practice Problem
1. Calculate the energy of a photon having a frequency of 3 x 1015/s.

Ep = h
Ep = 6.63 x 10-34 Js 3 x 1015/s = 2 x 10-18 J
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Practice Problem
2. Calculate the frequency of light having an energy of 2.0 x 105 J/mole.

Ep = h
2.0 X 105 J mole

mole

6.02 x 1023 photon

3.3 x 10-19 J = 6.63 x 10-34 Js

= 5.0 x 1014 /s
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Practice Problem
3. Calculate the energy of a photon with a wavelength of 575 nm.

= c
Ep = h

5.75 x 10-7 m = 3.00 x 108 m/s = 5.22 x 1014/s

Ep = 6.63 x 10-34 Js 5.22 x 1014/s

= 3.46 x 10-19 J
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Calculate the energy of the photon:

Photon wavelength = 2.35 x 10 -7 m

= c
2.35 x 10-7 m = 3.00 x 108 m/s = 1.28 x 1015/s

Ep = h
Ep = 6.63 x 10-34 Js 1.28 x 1015/s
= 8.49 x 10-19 J
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Calculate the min. energy to eject an electron:

Min. = 8.45 x 10 14 s-1.

Ep = h
Ep = 6.63 x 10-34 Js 8.45 x 1014/s = 5.60 x 10-19 J

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Calculate the extra energy of the electron:

8.49 x 10-19 J - 5.60 x 10-19 J = 2.89 x 10-19 J Calculate the velocity of the electron:

E = 1/2 m v2 2.89 x 10-19 J = (1/2) 9.11 x 10-31 kg v2

= 7.96 x 105 m/s
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Calculate the energy of the photon:

Ep = h
Ep = 6.63 x 10-34 Js 8.02 x 1013/s
5.32 X 10-20 J 6.02 x 1023 photon

photon

mole

= 3.20 x 104 J = 32.0 kJ

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Calculate the level number :

Ep = h
DE = -C [(1/n)2 - (1/n)2] -32. kJ = -1312 kJ [(1/n)2 - (1/8)2] n=5

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